Polychloro hydroxy derivatives of monocarboxy pyridines

ABSTRACT

NOVEL POLYCHLORO HYDROXY DERIVATIVES OF MONOCARBOXY AND DICARBOXY PYRIDINES, THEIR METHODS OF PREPARATION AND UTILIZATION AS PESTICIDES ARE DISCLOSED.

United States Patent Oflice Patented Mar. 21, 1972 ABSTRACT OF THEDISCLOSURE Novel polychloro hydroxy derivatives of monocarboxy anddicarboxy pyridines, their methods of preparation and utilization aspesticides are disclosed.

FIELD OF THE INVENTION This invention relates to new compositions ofmatter and methods for their preparation, and more particularly, to aclass of novel chemical compounds useful as pesticides includingherbicides, bactericides and fungicides.

SUMMARY OF THE INVENTION This invention presents novel compositions ofsubstituted pyridines of the general formula gi 011 N Where X ishalogen, n is an integer of 1 or 2 and R is like or unlike radicals ofthe carboxylate group including acids, salts and esters thereof, withthe provisions that R is not in the 3-position when the hydroxyl radicalis in the 4-position and n is one, and R is not in the 2-position whenthe hydroxyl radical is in the fi-positions and '11 1s one.

It is a principal object of this invention to provide novel chemicalcompositions having pesticidal properties enabling their applicationalone or in formulations to achieve such pesticidal utilization.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Compounds exemplary of theforegoing general structure include:

Trichlormh-hydroxypicolinic acid I o I! "605Dichloro-l+-hydroxyd1pico1inic acid dihydraveTrichloro-Zrhydroxyisonicotinic acid.

OH c1601 01 0E Dimeohyl dichloro -h-hyd.roxydipico1inate hydrate 01 c1.8 9 3,000 coca Potassium trichlcro-2-hydroxyisonicotinate 2 --0K 01 I 01cra Potassium trichloro-h-hydroxypicolinate While it is possible toapply the compounds in undiluted form to the locus to be protected orthe pest to be eradicated, it is more desirable to apply them inadmixture with either solid or liquid inert adjuvants. Thus, they can beapplied to the plants for fungicidal purposes, for example, by sprayingthe plants with aqueous or organic solvent dispersions of the compound.Similarly, wood surfaces can be protected by applying a protective filmof the compound by brushing, spraying or dipping, utilizing a liquiddispersion of the compound. The choice of an appropriate solvent isdetermined largely by the concentration of active ingredient which it isdesired to employ, by the volatility required in a solvent, the cost ofthe solvent and the nature of the material being treated. Among the manysuitable organic solvents which can be employed as carriers for thepresent pesticides, there may be mentioned hydrocarbons such as benzene,toluene, xylene, kerosene, diesel oil, fuel oil, and petroleum naphtha;ketones such as acetone, methyl ethyl ketone and cyclohexanone;chlorinated hydrocarbons such as carbon tetrachloride, chloroform,trichloroethylene and perchloroethylene; esters such as ethyl acetate,amyl acetate and "butyl acetate; the monoalkyl ethers of ethylene anddiethylene glycol, e.g., the monomethyl or monoethyl esters; alcoholssuch ,as ethanol, isopropanol and amyl alcohol; and the like.

The pesticidal compounds can also be applied to plants and othermaterials along with inert solid adjuvants or carriers such as talc,pyrrophyllite, attapulgite, kieselguhr, chalk, diatomaceous earth, lime,calcium carbonate, bentonite, kaolinite, cottonseed hulls, wheat flour,soybean flour, pumice, tripoli, wood flour, walnut shell flour andlignin.

It is frequently desirable to incorporate a surface active agent in thepesticidal compositions of this invention. Such surface active agentsare advantageously employed in both the solid and liquid compositions.The surface active agent can be anionic, cationic or nonionic incharacter.

Typical classes of surface active agents include alkyl sulfonates,alkylaryl sulfonates, alkyl sulfates, alkylamide sulfonates, alkylarylpolyether alcohols, fatty acid esters of polyhydric alcohols, ethyleneoxide addition products of such esters, addition products of long chainmercaptans and ethylene oxide, sodium alkyl benzene sulfonates having 14to 18 carbon atoms, alkylphenolethylene oxides, e.g., p-isooctylphenolcondensed with 10 ethylene oxide units; and soaps, e.g., sodium stearateand sodium oleate.

'The solid and liquid formulations can be prepared by any suitablemethod. Thus, the active ingredients, in finely divided form if a solid,maybe tumbled together with finely divided solid carrier. Alternatively,the active ingredient in liquid form, including solutions, dispersions,emulsions, and suspensions thereof, may be admixed with the finelydivided solid carrier in amounts small enough to preserve thefree-flowing property of the final dust composition.

When solid compositions are employed, in order to obtain a high degreeof coverage with a minimum dosage of the formulation, it is desirablethat the formulation be in finely divided form. The dust containingactive ingredient usually should be sufficiently fine that substantiallyall will pass through a 20-mesh Tyler Sieve. A dust which passes througha ZOO-mesh Tyler sieve also is satisfactory.

For dusting purposes, preferably formulations are employed in which theactive ingredient is present in an amount of to 50% of the total byweight. However,

concentrations outside this range are operative and compositionscontaining from .1 to 99% of active ingredient by weight arecontemplated, the remainder being carrier and/or any other additive oradjuvant which may be desired. It is often advantageous to add smallpercentages of surface active agents, e.g., 0.1 to 1% of the totalcomposition by weight, to dust formulations.

For spray applications, the active ingredient may be dissolved ordispersed in a liquid carrier, such as water or other suitable liquid.The active ingredient can be in the form of a solution, suspension,dispersion or emulsion in aqueous or nonaqueous medium. Desirably, 0.5to 1.0% by weight of a surface active agent is included in the liquidcomposition.

For adjuvant purposes, any desired quantity of surface active agent maybe employed, such as up to 250% of the active ingredient by weight. Ifthe surface active agent is used only to impart wetting qualities, forexample, to the spray solution, as little as 0.05% by weight or less ofthe spray solution need be employed. The use of larger amounts ofsurface active agent is not based upon wetting properties but is afunction of the physiological behavior of the surface active agent.These considerations are particularly applicable in the case of thetreatment of plants. In liquid formulations the active ingredient oftenconstitutes not over 30% by weight of the total and maybe 10%, or evenas low as 0.01%.

The pesticidal compounds of the present invention can be employed incompositions containing other pesticides, more especially fungicides,insecticides, and bactericides, e.g., phenothiazine, pyrethrum,rotenone, DDT, etc.

Preparation of the compounds In general the compounds of this inventioncan be prepared by reacting the suitable precursor, which is a compoundselected from the group of chlorinated cyanopyridines or chlorinateddicyanopyridines, with water in the presence of a base or an acid, orboth in sequence, depending upon whether the final product is to be a.salt or an acid. The bases employed are generally strong EXAMPLE 1Preparation of trichloro4-hydroxypicolinic acid A solution of 0.05 moleof tetrachloropicolinic acid and 0.05 mole of sodium hydroxide in 100ml. of water and 75 ml. of sulfolane was heated at -105 C. for 1 /2hours in a reaction vessel. The resulting reaction mixture was pouredinto Water, acidified with concentrated hydrochloric acid and filtered.The product was dissolved in a dilute sodium hydroxide solution,precipitated with concentrated hydrochloric acid and washed with watergiving a 29.8% yield of pure trichloro-4-hydroxypicolinic acid, whichdecomposes upon heating at 191-192" C. Elemental analysis showed 43.5%chlorine compared with a calculated value of 43.6%.

EXAMPLE 2 Preparation of dichloro-4-hydroxydipicolinic acid dihydrate Asolution of 0.05 mole of 3,4,S-trichlorodipicolinic acid and 0.05 moleof sodium hydroxide in ml. of water and 75 ml. of sulfolane was heatedat 90l05 C. for 1 /2 hours in a reaction vessel. The resulting reactionmixture was poured into water, acidified with concentrated hydrochloricacid and filtered. The product was dissolved in a dilute sodiumhydroxide solution, precipitated with concentrated hydrochloric acid andwashed with water giving a 71.5% yield of puredichloro-4-hydroxydipicolinic acid dihydrate melting at 293.5 to 295.5C. Elemental analysis showed 28.6% carbon, 2.4%

hydrogen, 23.9% chlorine, and 4.8% nitrogen. Calculation gives 29.1%carbon, 2.4% hydrogen, 24.6% chlorine, and 4.9% nitrogen.

EXAMPLE 3 6 on the slowest growing broadleaf (Zinnia). This requiresbetween 7 and 14 days depending upon the time of the year. When theplants (seedlings) have reached this stage of development, and one dayprior to spraying, the re:

maining portion of the soil plot is seeded as before, but

Preparation oftrichloro-2-hydroxyisonicotin1c aCld brgadleaves andgrasses are reversed,

The same procedure used in Example 1 was practiced The P2111S are then payed p.S.1., umformly coverhere, substituting tetrachloroisonicotinicacid for the tetramg the Surface 9 the S011 and the fohage wlth 40chloropicolinic acid, giving a 64.2% yield of pure triof testfofmulatlon 0 0 ppm.) at a dosage of 16 ch10ro-2-hydroxyisonicotinicacid, melting at 284-285.5 10 P0111145 Per acreh fhrmhlahoh cohtalhs0983 C. Elemental analysis showed the product contained chehhcal (098 Iffl acetone, 43.7% chlorine which is close to the theoretical 43.9% Stockemulslfier sohmon Tmon X455 m chlorine Calculated for this compoundwater by volume), and 18.0 ml. distilled water.

Two weeks after treatment, percent control 1s estlmated EXAMPLE 4 15 andinformation on phytotoxicity, growth regulation, and

Preparation f dimethyl i l 4 h other effects are recorded. Using thisprocedure, the foli li h d lowing results are obtained:

A solution of 0.1 mole of trichlorodipicolinic acid in 300 ml. ofmethanol was saturated with hydrogen chlo- Percent command other effectsride by bubbling HCI into the refluxing solution for five wPresmergellce hours. The solution was cooled and the product filtered.Dosage Broad- Broad- The product was purified by recrystallization frommeth- (lbs-I33 leaves Grasses leaves Grasses anol giving a 60.6% yieldof pure dimethyl dichloro-4- Dimethyldichlorothydroxydipicolinatehydrate melting at 125-127 C. On g lg g ggigicohn- 16 135 to elementalanalysis, 35.6% carbon, 2.7% hydrogen, 23.9% chlorine and 4.8% nitrogenwere found corresponding 1N0 buckwheat. to a calculated 36.3% carbon,3.0% hydrogen, 23.8% EXAMPLE 9 chlorine and 4.7% nitrogen.

EXAMPLES Soil drench and post-emergence foliage spray combination Tomeasure the foliage contact and soil drench herbiam following table andone or two equivalent weights of lauon i 150 is prepared 0.1- boththe.soll drenph potassium hydroxide and around 30 mL of water, all andfoliage spray treatments. Tl'llS formulatlon contains being charged intoa 125 ml. flask. The mixture was 35 0.36 g. of the test chemlcal (or0.36 ml. of a hqu1d), 6.0 heated to dissolve the solids and then theinsoluble were i stock emulsifier Solutlon 02 Tnton filtered off. Thewater was evaporated from the filtrate X 155 m Water by and 141'0dlsllned i and the residue was oven dried under vacuum. Table 1 ThePlants used for fins test are Planted m 31/2'mCh is a summary of thesepreparations with the first column Pots as follows: being the examplenumber, the second column listing 40 (a) Tomato, var. Bonny Best, oneplant per pot; the precursors, the third column listing the product, the(b) Garden bean, var. Tendergreen, four plants per pot; fourth columnlisting the melting point of the product, (c) Field corn, var. CornellM-3, four plants per pot; and the fifth column listing the analysis ofthe product. (d) Oats, var. Russell, 15 to 20 plants per pot.

TABLE 1 Percent chlorine Example Reactants Product mt 6? Found l a 5Trggh lgrg ggiy i g iggrggg nic acid and one Potassiumtrichloro-2-hydroxy'isonicotinate 347-350 37.6 37.9 6 Digi lpgfiyggpgxggigicggn i c a id and two Di p gt a ssiumdichloro-4-hydroxydipicolinate hy- 360 20.7 20.5 7 Dchlprgg h yggpglgpiggr c acid and one Mgxsl i gogassium dichloro-4hydroxydipicolinate360 22.5 23.0

qlllV 8 e.

EXAMPLE 8 The various test species are planted so that at treatmentPreand post-emergence tests in soil, broadleaf and grass species Thistest measures the preand post-emergence herbicidal activity of testchemicals applied to the foliage of seedling plants, as Well as to thesoil in which they are growing. Seeds of six species are planted in soilcontained in 9 x 9 x 2-inch aluminum cake pans filled to within /z-inchof the top with composted greenhouse soil. The seeds planted consist ofthree broadleaf species (buckwheat, Fagopyrum esculentum, turnip,Brassica rapa, and zinnia, Zinnia spp.) and three grass species(sorghum, Sorghum vulgare, Italian millet, Panicum ramosum, andperennial ryegrass, Lolium prenne). The soil in each pan is divided intotwo equal rectangular areas, and the broadleaves are seeded intoone-half of one of these areas and the grasses into the other half ofthe same area. The seeds are then covered uniformly with aboutone-fourth inch of soil and watered, after which they are removed to thegreenhouse and the test species are allowed to grow until one true leafis present time they are at the following stages of growth:

(a) Tomato-three to five inches tall;

(b) Beanthe first trifoliate leaf begins to unfold; (c) Cornfour to sixinches tall;

((1) Oatsthree to five inches tall.

In the soil drench treatment the soil surface of each pot (tomato, bean,corn, and oats) is drenched with 17.5 ml. of the test compound,resulting in an application of 64 pounds per acre. The four pots arethen sprayed simultaneously with the remaining ml. of formulation on arotating turntable in a hood at 40 p.s.i. This foliage spray contains2400 p.p.m. of chemical or about two pounds of active chemical pergallons of water solution. After the plant foliage dries, the plants areplaced in the greenhouse. The results are recorded fourteen days aftertreatment. Phytotoxicity is rated on the scale from 0, indicating noplant injury, to 11, plant kill and, additionally, stunting of the plantis rated on a scale of 1slight to 9severe. Chemicals found to give aphytotoxicity rating of 10 or more or a stunting rating of 9 on one ormore 7 of the test species are retested at lower rates. On retesting,the soil drench and foliage spray treatments are carried out as separatetests. Only those species on which suitable ratings were obtained forphytotoxicity or stunting or both contains 2400 ppm. of chemical orabout two pounds of active chemical per 100 gallons of water solutionwith dilution for lower concentrations tested. After the plant foliagedries, the plants are placed in the greenhouse. The

are retained for testing at lower dosages and remaining results arerecorded 14 days after treatment. Ratings are species are dropped fromfurther testing. Other responses based on a scale of 100 percent fortotal control of the such as formative effects (Fe), defoliant activity,growthblight. Chemicals found to give a very high rating in the regulantproperties, and chlorosis are recorded. Using this initial test areretested at lower rates. On retesting the procedure, the followingresults are obtained: soil drench and foliage spray treatments arecarried out as Phytotoxicity and other effects Soil watering Foliagespray Compound Lbs/a. P.p.m. To Be Co 0a To Be Co 0a'Irichlorot-hydroxypicolinio acid 64 2, 400 ll 8 10 11 10 8 10 Potassiumtrichloro-4-hydroxypicolinate S unts bean plan s at 2,400 ppm. for sprayand 74 lbs./acre for soil EXAMPLE 10 Rusticide Test This test determinesthe effective capacity of the test compounds as systemic cornrusticides. The heat-rust system employed is Uromyces phaseoli onPhaseolus vulgarius var. pinto which are tested in four-inch clay pots.A dosage of 45 ml. of the test formulation, equivalent to 45 mg. ofchemical or 64 pounds per acre, is drenched on each pot. This testformulation contains 0.1 g. (or 0.1 ml. if a liquid) of the testchemical, 4.0 ml. acetone, 2.0 ml. stock emulsifier solution (0.5%Triton X-155 in Water by volume), and 94.0 ml. distilled water. Theconcentration of toxicant in this formulation is 1000 parts per million.Lower concentrations of toxicant are obtained by diluting theformulation with distilled water.

Twenty-four hours after application of the test chemical, the plants areinoculated by atomizing onto the plant leaves a single aqueoussuspension containing the uredospore species. Subsequently the plantsare kept for an overnight incubation period at 60 F. and 100 percentrelative humidity. Pustule counts are made seven to ten days afterinoculation and effective control is reported as percent disease controlbased upon pustule development in non-treated control plants.Additionally, phytotoxicity of the plants by the test chemical is ratedby visual observation on a scale from 0, indicating no plant injury, to11, indicating plant kill. Using this procedure, the following resultsare obtained:

EXAMPLE l1 Bean halo blight Test formulations are examined for abilityto control bean halo blight (Pseudomonas Phaseolicola). A testformulation of 150 ml. is prepared for both the soil drench and foliagespray treatments. This formulation contains 0.36 grams of the testchemical, 6.0 ml. acetone, 3.0 ml. stock emulsifier solution (0.5 TritonX-l55 in water by volume), and 141 ml. distilled water.

The plants used for this test, garden bean var. Tendergreen, four plantsper pot, are planted in 3 /2 inch pots. At treatment time the beans havereached a stage of growth such that the first trifoliate leaf begins tounfold. Two of the bean plants per pot are inoculated by injection withthe bean halo blight using a hypodermic syringe. The organism is takenoff a slant culture medium.

In the soil drench treatment the soil surface of each pot is drenchedwith 17.5 ml. of the test compound, resulting in an application of 64pounds per acre. The test pots inoculated with the bean halo blight arethen sprayed simultaneously with the remain 80 ml. of formulation on arotating turntable in a hood at 40 psi. This foliage spray watenngseparate tests. Using this procedure, the following results areobtained:

Fungicides-foliage protectant and eradicant tests The tomato foliagedisease test measures the ability of the test compound to protect tomatofoliage against infection by the early blight fungus Alrernaria solani(E11. and Mart.) Jones and Grout and the late blight fungus Phytophthorainfestans (Mont) deBary. The method used employs tomato plants, 5 to 7inches high which are 4 to 6 Weeks old. Duplicate plants, one set foreach test fungus, are sprayed with various dosages of the testformulation at lbs./ sq. in. air pressure while being rotated on aturntable in a hood. The center of the turntable is inches from thenozzle of the spray gun. The test formulation containing the testcompound, acetone, stock emulsifier solution and distilled water isapplied at concentrations up to 2000 ppm. of the test chemical. Lowerconcentrations of toxicant are obtained by employing less toxicant andmore water, thereby maintaining the same concentration of acetone andemulsifier.

After the spray deposit is dry, treated plants and controls (sprayedwith formulation less toxicant) are sprayed while being rotated on aturntable with a spore suspen- 5101'! containing approximately 20,000conidia of A. solani per ml., or 150,000 sporangia of P. infestans perml. The atomizer used delivers 20 ml. in the 30-second exposure period.The plants are held in a saturated atmosphere for 24 hours at 70 F. forearly blight and F. for late blight to permit spore germination andinfection before removal to the greenhouse.

After two days from the start of the test for early blight and threedays for late blight, lesion counts are made on the three uppermostfully expanded leaves. The data are converted to percent disease controlbased on the number of lesions obtained on the control plants. Dosagesand percent disease control are given in the following table:

Percent disease control Systemic bactericidal test Test formualtions areexamined for ability to control tomato crown gall (Agrobacteriumtumefaciens). A test formulation containing 0.24 g. of the test chemical(or 0.24 ml. if a liquid), 4.0 ml. acetone, 2.0 ml. stock emulsifiersolution (0.5% Triton X-155 in water by volume), and 94.0 ml. distilledwater is prepared for both the soil drench and foliage spray treatments.Individual tomato plants, var. Rutgers, are planted in 3 /2 inch claypots and are 3 to 5 inches tall at treatment time. Stem punctureinoculation, at the cotylodonary node, with a cellular suspension of theAgrobacterium tumefaciens is made one to two hours prior to the soildrench and foliage spray treatment.

In the soil drench treatment, the test formulation is applied at thesoil surface of each pot; 17.5 ml. of the formulation being equivalentto a dosage of the test chemical of 64 pounds per acre with dilution forlower concentrations tested. Control is determined through visualobservation of tumor formation 10 to 14 days after treatment.

A rating of 90% is given to an estimate of complete control. Using thisprocedure, the following results are obtained:

It is to be understood that although the invention has been describedwith specific reference to particular embodiments thereof, it is not tobe so limited since changes and alterations therein may be made whichare within the full intended scope of this invention as defined in theappended claims.

What is claimed is:

1. As a composition of matter, a compound selected from the groupconsisting of trichloro-2-hydroxyisonicotinic acid, the lower alkylesters thereof and the alkali metal salts thereof.

2. Trichloro-2-hydroxyisonicotinic acid.

References Cited UNITED STATES PATENTS 3,251,849 5/1966 Tomita 260-295ALAN L. ROTMAN, Primary Examiner US. Cl. X.R.

UNITED S TATE S PATENT OFFICE CERTIFICATE'OF CORRE'CTION Patent No. '9',651,07O I I m Dated March 21, 1972 In fls). Charles E. Gr n-11:0

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby correcred as shown below:

Column 2, between the structural formulae on lines 35-45, read-Dipota.ssium dich1oro-4-hydroicypic olinate hydrate--.

Column 5, line 68, for "prenne", read ---perenne--. Column 8, line 17,for "74 lbs./a.cre", read ---64 1bs,/a.cre-1-.

Column 8, line 26, the value "6 should be on line 25 and the bracketremoved. v

Signed and sealed this 12th day of September 1972.

(SEAL) Attest:

EDV.'ARD M FLETCHER,JR. r ROBERT GOTTSCHALK Attestlng OfficerCommissioner of Patents FORM PC4050 (10-69} USCOMM-DC 60376-P69 u.5.GOVERNMENT Pmurme OFFICE: I969 0-366-384

